THREE LIQUID-LIQUID OPERATIONS Liquid extraction, the only operation inthis category, is basically very similar to the operations of gas-liquid contact described in the previous past. The creation of a new insoluble liquid phase by addition of a solvent to & mixture accom plishes in many respects the same result asthe creation of a new phase by the Addition of heat in distillation opecations, for example, or by addition of gas in desorption operations. The separations produced by single stages, the use of countercurrent cascades and reflux to enhance the extent of separation—all have their liqud-extraction counterparts. The similarity between them will be ‘exploited in explaining what liquid extraction can accomplish Certain differences in the operations nevertheless make it expedient to provide a seperate treatment for liquid extraction. The considerably greater change in mutual solubility of the contacted liquid phases which may occur ‘during passage through 2 cascade of stages requires somewhat different tech- niques of computation than are necessary for gas absorption or stripping. The considerably smaller differences in density of the contacted phases and their felatively low interfacial tension, compared with the corresponding gas-liquid systems, require consideration in the design of apparatus. The larger number of variables which apparently influence the rate of mass transfer in countercurrent equipment makes the correlation of design data much more difficult. For these reasons separate treatment is desirable, atleast for the present. Despite the increasingly extensive application of Hiquid extraction, thanks to its great versatility, and the extensive amount of research that has been done, it is nevertheless relatively immature unit operation. It is characteristic of such ‘operations that equipment types change rapidly, new designs being proposed frequently and lasting through a few applications, only to be replaced by others. Design principles for such equipment are never fully developed, and a reliance ‘must offen be pat on pilot plant testing for new installations.‘CHAPTER TEN LIQUID EXTRACTION Liquid extraction, sometimes called solvent extraction, is the separation of the constituents of a liquid solution by contact with another insoluble liquid. Uf the substances constituting the original solution distabute themselves differently between the to liquid phases, a certain degree of separation will result, and this can be enhanced by use of multiple contacts or their equivalent in the manner of 1s absorption and distilation. ‘A simple example will indicate the scope of the operation and some of its characteristics. Ifa solution of acstc acid in water is agitated with a liquid such as ethyl acetate, some of the acid but celatively litle water will enter the ester phase. Since at equilibrium the densities of the aqueous and ester layers are dlifecent, they wil seitle when agitation stops and ean be decanted from each ther. Since now the ratio of acid to water in the ester layer is different from that in the criginal solution and also different from that in the residual water solution, a certiin degree of separation will have occurred. This is an example of slagewise contact, and it can be carried out either in batch or in continuous fashion, The residual water can be repeatedly extracted with more ester to reduce the acid content sil farther, or We can arrange a countercurrent cascade of stages, Another possibilty is to use some sort of countercurrent continvous- contact dovice, where discrete stages are not involved. The use of reflux, as in isillation, may enhance the ultimate separation still further. Inall such operations, the solution which is to be extracted is called the feed, and the liquid with which the feed is contacted is the sofoent. The solvent-sich prodict ofthe operation is called the extrac, and the residual liquid from which solute has been removed isthe raffnate. More complicated processes may use two solvents to separate the compo- nents of @ feed, For example, a mixture of p- and o-nitrobenzoic acids can be ”478 ass-TRANSFER OPERATIONS separated by distributing them between the insoluble Hiquids chloroform and ‘water. The chloroform preferentially dissolves the para isomer and the water the ‘ortho isomer. This is called double.solvent, or fractional, extraction. Fields of Usefulness Applications of liquid extraction fall into several categories: those where extac- tion is in direct competition with other separation methods and those where it seems uniquely qualified. In competition with other mass-transfer operations Here relative costs are im Portant. Distillation and evaporation are direct separation methods, the products of which are composed of essentially pure substances. Liquid extraction, on the ‘other hand, produces new solutions which must in tum be separated, often by distillation or evaporation. Thus, for example, acetic acid can be separated from dilute solution with water, with difficulty by distillation or with relative ease by extraction into a suitable solvent followed by distillation of the extract. For the ‘more dilute solutions particularly, where water must be vaporized in distillation, extraction is more economical, especially since the heat of vaporization of most ‘organic solvents is substantially less than that of water. Extraction may also be attractive as an altemative to distillation under high vacuum at very low temperatures to avoid thermal decomposition. For example, long-chain fatty ‘acids can be separated from vegetable oils by high-vacuum distillation but more economically by extraction with liquid propane. Tantalum and niobium can be Separated by very tedious fractional crystalization of the double fluorides with potassium but with relative ease by liquid extraction of the hydrofluoric acid solutions with methyi isobutyl ketone. ‘As a substitute for chemical methods Chemical methods consume reagents and frequently lead to expensive disposal problems for chemical by-products. Liquid extraction, which incurs no chemical consumption or by-produet production, can be less costly. Metal separations such as uranium-vanadium, hafnium. zirconium, and tungsten-molybdenum and the fission produets of atomic-eneray ‘Processes are more economical by liquid extraction. Even lower-cost metals such 45 copper and inorganic chemicals such as phosphoric acid, boric acid, and the like are economically purified by liquid extraction, despite the fact that the cost of solvent recovery must be included in the final reckoning. For separations not now possible by other methods In distillation, where the vapor phase is created from the liquid by addition of heat, the vapor and liquid are necessarily composed of the same substances and are therefore chemically very similar. The separations produced then depend upon the vapor pressures of the substances. In liquid extraction, in contrast, the major constituents of the ‘wo phases are chemically very different, and this makes separations according, to chemical type possible. For example, aromatic and paraffinic hydrocarbonsLiq BxTRACTION 479 of nearly the same molecular weight are impossible to separaic by distillation because their vapor pressures are nearly the same, bat they can readily be separated by extraction with any of a number of solvents, e., liquid sulfur dioxide, diethylene glycol, or sulfolane. (Extractive distillation is slso useful for such operations, but itis merely extraction of the egpor phase with a solvent, whereas liquid extraction is extraction of the liquid phase. Frequently the same solvents are useful for both, as might be expected) Many pharmaceutical products, eg. penicillin, are produced in mixtures so complex that only liquid extraction is feasible separation device. LIQUID EQUILIBRIA Extraction involves the use of systems composed of at least three substances, and although for the most part the insoluble phases are chemically very Gifferent, generally all three components appear at least to some extent in both phases. The following notation scheme will be used to describe the concentra- tions and amounts of these ternary mixtures, for purposes of discussing both libria and materiat balances, Notation Scheme 1. A and B are pure, substantially insoluble liquids, and C is the distributed solute. Mixtures to be separated by extraction are composed of A and C, and B is the extraeting solvent. 2. The same letter will be used to indicate the quantity of a solution or mixture and the location of the mixture on a phase diagram. Quantities are measured bby mass for batch operations, mass/time for continuous operation. Thies, £ = mass/time of solution £, an extract, shown on a phase diagram by point £ R= mass/time of solution R, a raffinate, shown on a phase diagram by point R B= mass/time of solvent B Solvent-free (B-free) quantities are indicated by primed letters. Thus, E's mass Betreesolution/time, shown on a phase diagram by point E Ex E+ Ny) 3. x= weight Irdclion C in the solventJean (A-tich), or raffinat, liquids 1 = ‘eight fraction C in the solventerich (B-rich), or extract, liquids = s/(l ~ x) ~ mass C/mass non-C in the raffinate liquids Y= y/( = y)-= mass C/mass non-C in the excact liquids X ='weight Traction C in the raffinate liquids on a Betree basis, mass C/¢mass & + mass C)480 ASS-TRANSFER OPERATIONS Y = weight fraction C in the extract liquids on a B-free basis, mass C/(mass A+ mass C) N= weight fraction B on a B-free basis, mass B/(mass A + mass C) Subscripts identify the solution or mixture to which the concentration terms refer. Stages are identified by number. Thus, x3 — wt fraction C in the raffinate from stage 3, Y, « wt fraction C (B-free basis) in the extract from stage 3, ete. For other solutions identified by a letter on a phase diagram, the same letter is used as an identifying subscript. Thus, xy = wt fraction C in the mixture Mf. An asterisk specifically identifies equilibrium concentrations Where the condition of equilibrium is emphasized. Thus, yf = wt fraction C in the equilibrium solution E. 4, Throughout the discussion of equilibria, material balances, and stagewise calculations, mole fractions, mole ratios, and kilomoles may be consistently substituted for weight fractions, weight ratios, and kilograms, respectively. Equilateral-Triangular Coordinates ‘These are used extensively in the chemical literature to deseribe graphically the concentrations in ternary systems. It is the property of an equilateral triangle that the sum of the perpendicular distances from any point within the triangle to the three sides equals the altitude of the triangle, We can therefore let the altitude represent 100 percent composition and the distances to the three sides the percentages or fractions of the three components, Refer to Fig, 10.1. Each ‘apex of the triangle represents one of the pure components, as marked. The Perpendicular distance from any point such as X to the base 4B represents the percentage of C in the mixture at X, the distance to the base AC the percentage ‘of B, and that to the base CB the percentage of A. Thus x = 0.4, Any point on a side of the triangle represents a binary mixture. Point D, for example, is a binary containing 80 percent A, 20 percent B. All points on the line DC represent mixtures containing the same ratio of A to B and can be considered as ae © 8 ptgure 0. Equiterasrnnglr coordinates.Lig merRACTION 48 ‘mixtures originally at D to which C has been added. If R kg of a mixture at point R is added to E kg of a mixture at £, the new mixture is shown on the straight line RE at point M, such that invevge. Wisi ooen (10) Bue Ve Alternatively the composition corresponding to point M can be computed by ‘material balances, as will be shown later. Similarly, if a mixture at M has removed from it a mixture of composition , the new mixture is on the straight line EM extended in the direction away from F and located at R so that Eq. (10.1) applies. Equation (101) is ready esublshe. Refer to Fig. 102, which again shows A ke of mixture at R aided to E kg of aistare at E. Let M represen the Llograms of new mixture as well ts the ‘composition on te figure. Line RL. = weight faction Cin R= x, line MO = weight ration Cin ‘Mo Zand line E7 = weight faction Cin = xp A tual mate balance, Ree=M ‘A balance fr sommponeatC, ‘line RL) + Eline ET) = M(ine MO) Ruy + Bag = May liminating Mf, we get A lige EP line MO _ 6 ~ 24 7 line MO = line RL 3 ~ aq Dut line £7 ~ line MO = line EP, and line MO ~ ine RL = line MK = line PS. Therefore Aline BP _ tine ME B™ line PS ~ Tae RM ‘The following discussion is limited to those types of systems which most {frequently occur in liquid-extraction operations. For a complete consideration of ‘the many types of systems which may be encountered, the student is referred to ‘one of the more comprehensive texts on the phase rule [51]. aT ‘3 Mw 102 The mixtre rule,(482 MASs-TRANSFER OPERATIONS ‘Systems of Three Liquids—One Pair Partially Soluble This is the most common type of system in extraction, and typical examples are ‘water (A)-chloroform (B)-acetone (C) and benzene (A)-water (B)-acetic acid (©. The triangular coordinates are used as isotherms, ot diagrams at constant temperature. Refer to Fig. 10.34, Liquid C dissolves completely in A and B, but A and B dissolve only to a limited extent in each other to give rise to the saturated liquid solutions at L (A-rich) and at K (B-tich). The more insoluble the liguids A and B, the nearer the apexes of the triangle will points L and.K be located. A binary mixture J, anywhere between L and K, will separate into two insoluble liquid phases of compositions at L and K, the relative amounts of the phases depending upon the position of J, according to the principle of Eq, (o., Curve LRPEK is the binodal solubility curve, indicating the change in solubility of the A- and B-rich phases upon addition of C. Any mixture outside this curve will be a homogeneous solution of one liquid phase. Any ternary ‘mixture underneath the curve, such as M, will form two insoluble, saturated liguid phases of equilibrium ‘compositions indicated by R (A-tich) and E (B-rich). The line RE joining these equilibrium compositions is a tie line, which ‘ust necessarily pass through point M representing the mixture as a whole. ‘There are an infinite number of tie lines in the two-phase region, and only a few are shown. They are rarely parallel and usually change their slope slowly in one direction as shown. In a relatively few systems the ditection of the tie-line slope changes, and one tie line will be horizontal. Such systems are said to be solutropic. Point P, the plait point, the last of the tie lines and the point where the Actich and Berich solubility curves merge, is ordinarily not at the maximum, value of C on the solubility curve. ‘The percentage of C in solution is clearly greater than that in R, and itis said that in this ease the distribution of C favors the B-rich phase. This is me of wre nor eo | oe He wpe iw Eto) wo Hheame Un Peas utiona ee Figure 103 Sywiem of three tiguds, A and B partly miscible